Method of bonding graphite articles with iron-base brazing alloys



7 7 5 a 7 7 1 3 S E as L Y HO Tum E A m Anmm RHI u mmw m m FIAF DB owmm T MH ADAWIF wm HW T E M April 13, 1965 INVENTORS. TADATO FUJIMURA a YOSHIO ANDO their A TTORNEYS United States Patent Ofiicc 3,177,577 Patented Apr. 13, 1965 This invention relates to a method of bonding graphite articles by means of iron-base brazing alloys.

The principal object of this invention is to obtain an extremely firm and leak-tight joint between graphite articles, and more particularly graphite blocks to be used in nuclear reactors.

In nuclear reactors, a large amount of graphite is used as thematerial for the moderator of fast neutrons and also as the canning material of fuels. Since graphite is a non-metallic substance and brittle, its shaping and working are diflicult in the construction and design of nuclear reactors and the perfect bonding of graphite articles has been considered almost impossible up to the present time. The "conditions of bonding graphite articles used in nuclear reactors are as follows:

(1) The smallest possible amount of brazing material should be used in order to reduce the absorption of neutrons.

(2) Possibility of leak-tight brazing joint. (3) 'Less corrosion due to the colant (in order to effectively utilize the high corrosion resistance of graphite the corrosion resistance should be particularly high).

(4) Sufiiciently high bonding strength should be main- I tained at high temperatures (thoughgraphite is very stable at high temperatures it is desirable that the bonded portion might have such strength effective at a temperature of about 800 C. in the reactor).

(5) Sufliciently high bonding strength should be main .tained'during the whole thermal cycle of operation (since graphite has a small coeliicient of thermal expansion the brazing material should have a comparable coefiicient of thermal expansion) (6) Bonding proces should be simple and adapted for mass production. a

(7) Accuracy of dimensions should be positively assured.

Various kinds of cementing materials have been used in Japan for the bonding of graphite, but such materials could notsufliciently fulfill the above mentioned condi- 'tions (1), (2),'(3), (5) and (7).

In some foreign countries, the brazing is effected by using zirconium and titanum as the brazing material, but such metals are highly oxidizable materials so that the brazing process is very difficult, is costly and is not very practical.

The present invention has been achieved after the result of various investigations and experiments for obviating the above described defects, and has been found a very splendid bonding process compared with the heretofore known process of using cement and other metallic brazing materials and satisfies the above mentioned conditions (1) to (7) for bonding graphite articles to be used in nuclear reactors, by using iron-base alloys as brazing material. I

According to this invention, the brazing alloys consist of iron and one or more of the followingchromium, nickel, molybdenum, tungsten, titanium, zirconium and carbon.

For instance, the following alloys are preferable:

Fe-Cr-C, Fe-Ni-C, Fe-Ni-Cr-C, Fe-Cr-Ni-Mo-C The following range of compositions have been found applicable to the present invention.

Nl M0, W, Ti 7 0 Fe in practice.

The addition of 10 to 50% nickel to the iron'base increases its strength and corrosion resistance athigh temperatures, and the iron-Ni alloy has a very small thermal coefficient of expansion that is nearly equal to the coeflicient of thermal expansion of graphite so that the brazing result is very good. On the other hand, the coefiicient of thermal expansion increases rapidly at a range less than 10% or more'than 50% nickel and the adhering properties become worse so that according to the present invention 10 to 50% by weightof nickel in the brazing alloy was found very practical.

The brazing iron-base alloys containing chromium, and nickel with or without the addition of molybdenum, tungsten, zirconium or titanium can also beused in this invention. In this case, the composition of-16 to 30% of Cr, 6 to 25% of Ni, 0 to 4% of Mo, W,-Ti or Zr, less than 0.2% of C, with the remaining portion being of Fe (all by weight percent) is most suitable. Theaddition of molybdenum, tungsten, titanium orzirconium further maintains the high temperature strength of the alloy.

The thermal characteristics of the brazing alloys are as follows:

Alloys Coefficient of Melting Point Corrosion Magnetic High temperature Tension test thermal expansion 7 resistance property strength at room temp.

(1) Fe-Cr 10 to 13 10- 1,430 to 1,510 0... Good. None SuliicleCnt up to No breaking.

700 (2) Fe-Cr-Ni-Mo 17 to 20 10- 1,370 to 1,430 0... Better do stgfggitglt up to Do. (3) Fe-Nl 2 to 10 10- 1,420 to 1.470 0... do do "do a- Do.-

The brazingaccordingto this invention can 'becarried out by different processes such as (1) induction brazing and (2) arc-brazing.

(1) The induction brazing pieces of a brazing wire or powders of the above mentioned brazing material, in a groove or. recess formed between the adhering portion of graphite articles. The assembly is heated in of 10* to 10* mm. Hg or in an'in'ert such as argon, helium or nitrogen, or in an atmosphere cfjactiVe ammoniumbr'hydrogen to a bonding temperaturefof from 1,200 to 1,600 C. a

Thej st'r 'ength test of the brazed joint was by preparing graphite rods put together in I tior'ishipjaridbonded inavacuu'm of 5 10-r mm. Hg at -1,3 50 C. by using the brazingmaterial of this invention.

carried out may be effected by filling a vacuum furnace under a vacuum gas atmosphere butt joint rela- -welding is -carried outfby blowing out shielding-gas through the torches.

As the kind of shielding gas for carrying out the above brazing process, argon, helium, carbon dioxide gas, ni-

trogen or hydrogen is most suitable. Such gas may be issued through the brazing torch in'the open air, or the brazing may be carried out in an air tight chamber enclosing theabove shielding gas;

A tension testpiece was taken from the graphite rod' thus bonded and subjected to, the high temperature tension test a The results'showed v I at 900 Q, in, an argon atmosphere. that'the' sample did not break down at the joint portion but was broken along the body of the materiaL. 7'

The bending'test accord'ng to the Japanese Industrial Standard-wascarried out at room temperature for .the joint portion of the brazed graphite rods, whichpassed the test.

As to theneutron economy in a reactor the fresultsof calculations showed that if the brazing material is about l/2,500 of the mass of'graphite used, the neutron absorption cross section-of the" graphite -structure increases about 10%. This shows. thatv the use. of the brazing materialfor "joiningithe structures of a reactor would not cause-'troublesTin.thldesign of internal construction of the reactor. 7

by in arc"brazin 'iu'sing any ofthe above mentioned brazing alloys; in an open dation of the graphite andbra'zing material, using a shielded arc brazing torch, thereby melting the brazing parrying out the method of this invention the following ,twomethods may be used:

materialsby the :lieat" developed by the electric arc. In

brazedlas an anode '(or cathode) the electrode'enueeaaae in the torch.

.(b). Another"method uses gas shielded brazing torch in jwliich'"are ei'i'clo'sed a'positive electrode and a between-these electrodes while shielding gasis blown out tt tqrcht a V 1 For-,aiflbtter understanding of the manner of carrying graphite articles can alsobe unitedtogether atmosphere, by" preventingoxi- Qne method is to use the graphite articlesto be negative ,ele trode, with anTelectric arc being'generated j I i i i i i v zdut'rthe arcbrazin'g of this invention reference is had to L.

thehaccompanyingidrawings, in which,

blocks to be welded, and 2 a: groove "or ljter mmaheleet" 1y Icoh'riectedto the graphite block, f5

to be brazed, r2 isra groove formed betweenvthe'graphite yin'g tout arc 'br'azing of I graphite 1 v FrG; -1;- the reference numerals 1+1 'rep v v a a etweenthegrfaphite blocks 1 and 7 3 is a V ards'tlie oin'ed portion, 4' aconducting' "tion was'rnore than 150 kg./cm.

When graphite plates or pipes were using a brazing material of iron-base-alloys consisting of 36% nickel; by weight and 64% iron; by weight by a electric arc the following conditions are usedzl Arc voltage: 11c; 30 to 50 volts.

Arc current; DC. 100 to 200 amps, Shielding gasz'Argon, Gas'flowzfltl to 2 0 litrs/niinute.

As to the neutron economy in a reactor, the results of V calculations showed that when thebrazing alloy was about t 1/ 3,000of the mass of graphite is used the neutron absorpbondediby the method of this invention has improved characteristics v V as shownbytheffollowing: ('1) The results or static bending test of'the'bonded joint showed that the bending strength ofjthe bondedpor- 2') When the sample is heat (1 to 700*" C. and then quickly cooled in air no crack occurred in the bonded p j i v t k t (3)' -As the result of leakage tests of the joint no leakage was found., a

', By using the brazing alloys for the arc'brazing of graphitefarticles' 'diflicul'ties in shaping'and working of graphite, articles can 'beminimized, so that the-utilization of "graphite in; nuclear ieactors can be increased.

1; 'A 'method of'jo'ining graphite articles by'means of iron-base alloys a brazing material, I which comprises carryingJ out the jbnazirigby 'filling a recess formed between abutted edg s, on the upper surfaces of two graphite articlesto be joined 'withffus'ed brazing material of iron- "b'a'se alloys consisting of lQ'ito 50% by weight of nickel, less than 012% of carbonand the remaining substantially -of iron, by heatingithe brazing material to a temperature .of from 1,200 to by anelectric arc in-a shield- '2. The method of. claim 1 ,whereinjthe'electric arc is I a enerated-between 'the' ra hit' and "braz' t h. FIGSLI and j 2"areperspective views illustrating two g g p e a mg 3. The method of claimvrl wherein the electric arc is generated between;two electrodes' carried in a brazing =toreh.

*4. A'methdd of welding graphit surf es w i h 0 prises filling, a; recess formed; between abutting edges of 'two grap'hite surfaces with a 'niolten alloyconsisting of '16 'to 3'0% by weight of chromium,u 6 to'25% nickel, f0 to 4%,ofan' element fron'r'the grou'ppconsisting of molybaenu'm'; tungsten, titanium,'.and zirconium, less thanlO.2%

carbon and the balance substantially, of iron, said alloy :being'me te y n e w s ginehieldi g s m??- phere.

blocks, such recess facilitating soundibondingflfa and 4 are torches lincluding positive andnegative' electrodes re-' "spectively directed to the: jbilied iioi'tidfi, and 5 is; the

brazed material" after the bonding is ifinished'gand fi fi 1 represent electrodes, and a the brazing filler wire-accord:

ing to this invention; case of FIG," 2, je1ectric arcs are 5. A method ofiweldinggraphite surfaces which compr ises jfilling arecless formed between abutting edges of two"g"r'a;phite sn faees'with 'a' rnolten alloy consisting of 'l6 1to" 30 by weight of chromium', 6 to, 25% nickel, 0 -ft'o;4%' of an 'elementflfroni ithe group consisting of "molybdenum,-tungsten, titanium and; zirconium, less than Y 0.2% .vcarbon.audlithebalancie,substantially' of iron, said bonded together by v V 5 6 alloy being melted by an electrical induction in a shield- 2,739,375 3/56 Coxe 29504 X ing gas atmosphere. 2,770,030 11/56 Carpenter et a1. 29504 X References Cited by the Examiner FOREIGN PATENTS UNITED STATES PATENTS 5 587,622 11/ 9 Canada 1 946 05 3 Caflett JOHN F. Primary Examiner.

2,431,975 12/47 Yockey. WHITMORE A. WILTZ, Examiner. 

1. A METHOD OF JOINING GRAPHITE ARTICLES BY MEANS OF IRON-BASE ALLOYS AS BRAZING MATERIAL, WHICH COMPRISES CARRYING OUT THE BRAZING BY FILLING A RECESS FORMED BETWEEN ABUTTED EDGES ON THE UPPER SURFACES OF TWO GRAPHITE ARTICLES TO BE JOINED WITH FUSED BRAZING MATERIAL OF IRONBASE ALLOYS CONSISTING OF 10 TO 50% BY WEIGHT OF NICKEL, LESS THAN 0.2% OF CARBON AND THE REMAINING SUBSTANTIALLY OF IRON, BY HEATING THE BRAZING MATERIAL TO A TEMPERATURE OF FROM 1,200 TO 1,600*C. BY AN ELECTRIC ARC ILN A SHIELDING GAS ATMOSPHERE.
 2. THE METHOD OF CLAIM 1 WHEREIN THE ELECTRIC ARC IS GENERATED BETWEEN THE GRAPHITE AND A BRAZING TORCH. 